Anilide carbamates as algicidal agents

ABSTRACT

WHEREIN R1 is hydrogen or alkyl, R2 is alkyl, alkynyl, cycloalkyl, allyl, phenyl, 3,4-dichlorophenyl or benzyl and R is alkyl, haloalkyl, alkenyl, or cyclopropyl as algicidal agents.   This invention relates to the utility of certain anilide carbamates of the general formula:

United States Patent [1 1 Baker et al.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

22 Filed: Dec.26, 1972 211 Appl. No.: 318,316

Related US. Application Data [63] Continuation-impart of Ser. No. 119,852, March 1,

1971, abandoned.

[52] US. Cl 7l/67, 71/106, 71/111,

260/468 C, 260/471 C, 260/479 C [51] Int. Cl A01n 9/20 [58] Field of Search 71/67, 106, 111

[56] References Cited UNITED STATES PATENTS 3,535,101 10/1970 Boroschewski 71/111 3,404,975 10/1968 Wilson et al 71/111 FOREIGN PATENTS OR APPLICATIONS 686,239 -2/1967 Belgium 71/106 [4 1 Feb. 19, 1974 688,103 11/1967 Belgium 71/106 Primary ExaminerLewis Gotts Assistant ExaminerCatherine L. Mills Attorney, Agent, or Firm-Harry A. Pacini; Daniel C. Block; Edwin H. Baker [57] ABSTRACT This invention relates to the utility of certain anilide carbamates of the general formula:

wherein R is hydrogen or alkyl, R is alkyl, alkynyl, cycloalkyl, allyl, phenyl, 3,4-dichlorophenyl or benzyl and R is alkyl, haloalkyl, alkenyl, or cyclopropyl as algicidal agents.

39 Claims, N0 Drawings 1 ANI LIDE CARBAMATES AS ALGICIDAL AGENTS This application is a continuation-in-part of copending application Ser. No. 119,852, filed Mar. 1, 1971 now abandoned.

This invention relates to the utility as algicidal agents for the control of algae when used in an algicidally effective amount of certain substituted anilide carbamates of the general formula:

R1 OJLN wherein R is hydrogen or alkyl, R is alkyl, alkynyl, c y

cloalkyl, ally], phenyl, 3,4-dich1oropheny1 or benzyl and R is alkyl, haloalkyl, alkenyl, or cyclopropyl. It was found that these compounds have an algicidal effect and provide beneficial results in controlling the growth of algae.

Controlling the growth of algae by employing the compounds described herein can be accomplished by applying an algi'cidally effective amount to the environment in which algae growth is encouraged. The compounds may be applied to any environmental area which is a host to algae or susceptible to algae attack and growth. By controlling, it is meant the inhibition and prevention of the growth of the organism to be 30 halogen substituted alkyl radicals containing from one,

to six carbon atoms, inclusive, such as monochloromethyl, dichloromethyl, trichloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, pentachloroethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, fluoromethyl, fluoroethyl, chlorofluoromet hyl, chlorofluoroethyl, monofluorotetrachloroethyl, and the like.

The term alkenyl as used herein contemplates alkenyl radicals containing at least one double bond and from two to four carbon atoms, inclusive, such as vinyl, allyl, 2-methy1viny1, butenyl-l and the like. The term alkynyl as used herein preferably includes those members containing at least one triple bond and from three to six carbon atoms, inclusive.

The following compounds in Table I can be used, for example, according to the invention hereindescribed.- Compound numbers have been assigned and are used controlled. throughout the balance of this applicatlon.

TABLE 1 1 O-Jl-N NH-fi-R COMPOUND NUMBER R R R PHYSICAL CONSTANT m.p.

(0C) or "0710 l H CH CCl 165-172 2 H CH CH=HCH; 156-158 3 H i-C -,H, C H 198-199 4 11 n-C H c 11, -133 5 1-1 cyclohexyl C 11 156-159 6 c 11 0,11,, 0,11 77-78 8 n-c,1-1, n-C H, cm, 55-59 9 H 3 ,4-d1C1O C H, 185-188 10 H sec-C 11 C H 186-188 1 1 H z- H, c 11 210-213 1: 11 c1-1,c1-1=cH, 0 11, 136-142 13 H C H 1-C H 164-168 14 H n-C H i-C H, 153 15 H phenyl CH 170-173 16 H t-C H sec.-C H 139-141 17 H 3 3 -157 18 H C 11 CH=CHCH 137-140 19 H C H cyclopropyl 191-194 20 H i-C H CH=CHCH 168-173 21 H i-C H cyclopropyl 210-214 22 H n-C H cyclopropyl -163 23 H n-C H CHCICH 153-157 24 H n-C,H,, CH=CHCH 178-183 25 H n-C H CCl -173 26 H n-C ,H C H 146-149 27 H C H CCl 184-188 28 H i-C H CCl 203-210 29 H i-C H CHCICH; 216-218 30 H n-C H, CH(C H 118-120 31 H n-C H C H 108-113 32 H benzyl C 11 159-161 33 n-C H n-C H, C(CH C H-, 1.5081 34 c 11 n-C H (:(cH, ,C 1-1, 1,5170

TABLE I-Continued COMPOUND NUMBER R R R PHYSICAL CONSTANT mp.

(C) or 35 n-C.H., n-C.H,, C CH .,),C,,H 1.5105 36 H cyclohcxyl CH 1 168-173 37 H H(C2 2 166-170 38 H CH(CH CH CH(CH C,H,, 148-151 39 H :i) s)2 n CzHr, 1825-1875 40 H .1 .1 1 1 154-156 4] H 2 :i)-z z s 144-146 42 H cyclopentyl C2H5 173-177 43 CH i-C H C H 15349 44 C H i-C H, C.H Gum 45 C2H5 4 n z s 1.5290 46 H C CHm-C 5 CH C,H 156-158 47 CH CH(CH, -C CH C H 1.5348 48 H 3 1 (CH.),C.H1 128-130 49 H t-C..H., C(CH C H, solid The compounds mentioned thus far, and those conof the formula templated, can be produced, for example, according to 0 the following methods. 0 ll C1 The compounds herein disclosed are prepared by one of several methods. When R is hydrogen and R is alkyl, cyclohexyl, allyl, phenyl, 3,4-dichlorophenyl or benzyl, a convenient method applicable to preparing the compounds is the reaction between an appropriate substituted-m-amido phenol and an appropriate isocyanate.

An organic solvent, e.g., chloroform, methylene chloride, ether, dioxane or acetone, can be employed as a reaction medium. Acetone and homologous ketones are found to be particularly convenient when the mhydroxy alkylanilides are used because such anilides are more soluble in these solvents than in other less polar inert solvents. A tertiary amine, preferably triethylamine, is used in catalytic amounts to promote the reaction. Reaction temperatures are employed that permit operation in the liquid phase. Said reaction temperatures are between room temperature and reflux temperature of the solvent, if any is used. When R is alkyl and R is alkyl, cyclohexyl, allyl, phenyl, 3,4- dichlorophenyl or benzyl, one convenient method applicable for preparing the compounds is the reaction of an appropriately substituted carbamoyl chloride and a 3-hydroxy-anilide.

and, either a primary or secondary amine, e.g., the formulae H or Eli-N These later reactions, employing a carbamoyl chloride or a chloroformate, are preferably carried out in the presence of a hydrogen halide acceptor, such as triethylamine, or an excess of an amine starting material, pyridine, picoline, sodium carbonate, potassium carbonate and the like. Temperatures which are employed in these reactions permit operation in a liquid phase and are between about 0C. and reflux temperature of the solvent, if one is used.

The following illustrated examples describe in detail, without restriction thereto, the preparation of representative compounds.

EXAMPLE 1 Preparation of m-(N-methylcarbamoyloxy)acetanilide In ml. of chloroform, as a solvent, are brought together 15.2 g. of m-hydroxyacetanilide and 6.0 g. methyl isocyanate. To this solution is added 0.3 ml. of triethylamine and a trace of dibutyl tin dilaurate as catalysts. The mixture is refluxed and stirred for 1 hour. A solid product is formed during this period. The solid is separated by filtration. There is obtained 19.2 g. (93.65 yield) of the title compound, m.p. l55l57C.

EXAMPLE 11 Preparation of m-(N-isopropylcarbamoyloxy)propionanilide In 60 ml. acetone in a round bottom flask equipped with a stirrer, reflux condenser and dropping funnel is dissolved m-hydroxy-propionanilide (3.3 g.). To this solution is added 0.4 ml. of triethylamine. Isopropyl isocyanate (3 g.) is added gradually with good agitation of the reactants. The precipitation of the product indicates that the reaction is proceeding satisfactorily. When all the isocyanate is added, the mixture is refluxed for 20 minutes, then cooled to room temperature and allowed to stand overnight. A white solid product is recovered by filtration. There is obtained 4.] g. of the title compound, m.p. l98199C.

EXAMPLE lll the crude product is 27.5 g., m.p. 5 l-59C.

EXAMPLE IV Preparation of 3-propionamidophenyl chloroformate A solution of 10.1 g. (0.1 mole) of phosgene in 25.9 g. of toluene is prepared and 25.6 g. of this solution is added to 100 ml. of toluene, and 16.5 g. (0.1 mole) of 3'-hydroxy propionanilide is added and dispersed. Triethylamine, 10.1 g. (0.1 mole), is added dropwise and a mildly exothermic reaction results. The temperature is kept under 30C., with cooling in a water bath. After approximately 70 percent of the triethylamine is added, the remaining phosgene solution is added all at once. The addition of triethylamine is continued. When addition is complete, about ml. of acetone is added and a nearly homogenous yellow solution resulted. It is filtered to remove about 4 g. of starting material and evaporated to a viscous yellow liquid. There is obtained 18.8 g. of the title compound, m, 1.5437. Calculated for c, 11,.,o,Nc1; C1 15.67 percent, found 15.43 percent. Preparation of m-(N-t-butylcarbamoyloxy)propionanilide Eighteen and two-tenths (18.2) grams of 3-propionamidophenyl chloroformate in methylene chloride solution (0.08 mole) is cooled to 0C. and t-butylamine, 24.2 g. (0.16 mole), is added with gentle shaking. A very exothermic reaction took place. The flask is cooled in an ice bath and after 5 minutes it solidifies. The product is treated with 70 ml. of benzene and 50 ml. of cold water is added with stirring. The mixture is filtered and the filter cake is washed with cold water. A nearly white solid is obtained, m.p. 158-160C. The product is recrystallized four times from ethyl acetate. There is obtained 2.5 g. of the title compound, m.p. 2l02l2C.

EXAMPLE V Preparation of 3-(N-methyl carbamoyloxy)trichloroacetanilide Methyl isocyanate, 3.2 g. (0.055 mole) is added to 12.7 g. (0.05 mole) of 3'-hydroxy trichloroacetanilide in 150 ml. of methylene chloride containing approximately 0.5 g. of triethylamine as a catalyst. The solution is refluxed for 1 hour. The product precipitates after 30 minutes. The mixture is cooled, and the product filtered off. It is washed with petroleum ether and dried in a vacuum oven. There is obtained 13.3 g. percent of theory) of the title compound, m.p. 165-l72C.

EXAMPLE Vl Preparation of 3-(N-butylcarbamoyloxy)crotonanilicle.

Nine and nine-tenths (9.9) grams of 3'- hydroxycrotoanilide is dissolved in ml. of acetone, 6 grams of butylisocyanate is added, followed by 4-5 drops of dibutyl tin dilaurate and approximately 100 mg. of triethylenediamine and the mixture heated at reflux for 2 hours. The mixture is poured into water and the product collected and dried. Yield is 10.8 g., m.p.

EXAMPLE Vll Preparation of 3 N-ethylcarbamoyloxy )cyclopropanecarboxanilide Ten and six-tenths (10.6) grams of 3-hydroxycyclopropanecarboxyanilide is dissolved in 100 ml. of acetone and treated with 4.7 g. of ethylisocyanate, 4-5 drops of dibutyl tin dilaurate and approximately 100 mg. of triethylenediamine. The mixture is heated at reflux. After three-fourths hour of reflux, the product crystallizes from the refluxing acetone. The mixture is cooled and the product filtered off. Yield is 11.6 g., m.p. l9ll94C.

The following examples are given for the purpose of illustrating the effects according to the instant invention:

ALGICIDAL TEST PROCEDURE Sufficient candidate toxicant is diluted in acetone to give an 0.5 percent mixture which is then diluted into 20 milliliters of warm modified Jack Meyers Agar Medium (Algae Culture from Laboratory to Pilot Plant, 1953, Page 94). The dilutions are such as to give concentrations of 0.5 and 1.0 ug/ml. of the test compound in 20 X 100 mm. petri dishes. After the agar solidifies, separate petri dishes are innoculated with the desired organism, such as Scenedesmus obliquus or Chlorella pyrenoia'osa. The innoculated samples are then allowed to grow at room temperature under fluorescent lamps using a 14 hour light period each day. After one to two weeks, depending upon the growth of the untreated controls, the results are recorded as to the level necessary to control the specific organism. The results obtained with representative compounds and their concentrations are given in Table 11.

TABLE II ALGlClDE TEST COMPOUND NUMBER Scenedesm us obliquus (concentration, pg/ml.)

TABLE ll -Continued ALGICIDE TEST COM POUN D N UM BER Scenedesm us obliquur (concentration, pg/ml.)

( denotes partial control at the indicated concentration.

Compounds Number 5, l7 and 38 controlled Cholorella pyrenoidosa at 10 ug/ml. Compound Number 39 also gave partial control of Chlorella pyrenoidosa at 1.0 ug/ml.

The manner in which the water area may be treated for the control of algae will vary with the specific problems encountered. An acute problem in the storage and utilization of industrial process water is the fouling of such water and systems in which the water is used by the growth of algae. Entire areas such as a pond or lake may be treated. Drainage ditches and other waterflowing sites may be treated.

In addition to use in ponds and lakes, this invention is applicable to the control of algae in industrial cooling towers and other water recirculating systems as used in paper manufacturing processes, for example.

The substances to be employed according to the present invention can be used as such or in the form of formulations with carrier vehicles. Examples and emulsifiable concentrates, spray powders, pastes, soluble powders, and the like. Suitable carrier vehicles or assistants are mainly: Solvents, such as, optionally chlorinated, aromatic hydrocarbons (e.g., xylene, benzene, chlorobenzenes), paraffins (e.g., petroleum fractions), alcohols, (e.g., methanol, ethanol, butanol), amines (e.g., ethanolamine, dimethylformamide), as well as water; finely divided solid carriers, for example, natural and synthetic stone meals or powders (kaolin, alumina, chalk, i.e., calcium carbonate, talc, highly disperse silicic acid, silicates, e.g., alkali silicates); emulsifiers, such as non-ionic and anionic emulsifiers (e.g., polyoxyethylene fatty acid esters and polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) especially magnesium stearate, sodium oleate, etc., and dispersing agents such as lignin, sulfite waste liquors and methyl cellulose.

As already mentioned above, the active compounds or agents to be employed according to the instant invention can be present in the aforesaid formulations in mixture with one another and with other known active substances.

The algicidal compositions of the invention also comprise aqueous emulsions. The aqueous emulsions can be prepared by dissolving a surfactant of the type noted hereinabove and pouring the emulsifiable concentrate so obtained into water with vigorous agitation. The aqueous emulsions of the invention can also be prepared by dissolving the active ingredient in a watermiscible solvent such as Carbitol (diethylene glycol monoethyl ether), acetone, 21 lower alkanol, Cellosolve (ethylene glycol monoethyl ether), dioxan, and the like, if desired, in association with a surfactant such as noted above, to obtain an emulsifiable concentrate which is poured into water with vigorous agitation. The aqueous emulsions of the invention can also be prepared by dissolving the active ingredient and a surfactant such as noted above in an organic solvent which is immiscible with water. The resulting emulsifiable concentrate is then admixed with waterwith vigorous agitation to form an emulsion. The water-immiscible organic solvents which are suitable for use include cyclohexanone, summer oils, aromatic hydrocarbons such as benzene, toluene, xylene, and high-boiling petroleum hydrocarbons such as kerosene, diesel soil, and the like.

The aqueous emulsions of the invention can be supplied to the user in the form of the emulsifiable concentrates described above which require dilution with water before use. Both the concentrated compositions and the diluted compositions are included within the scope of the present invention.

Formulations contain, in accordance with the present invention, in general from 0.1 to 95, preferably 0.5 to 90, percent by weight of active compound or agent. The agents according to the present invention or their preparations are applied in the usual way, e.g., by spraying, dusting, sprinkling or atomizing. The active substances can be applied, according to the purpose in view, in a concentration of 5 to 0.0005 percent. In special cases it is, however, possible or even necessary to go below or above these concentrations. The remainder of active algicidal composition being an adjuvant which can be a liquid extending agent or surface active agent, but preferably is an admixture thereof.

Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains.

What is claimed is:

1. The method for inhibiting and preventing algae growth in water, which comprises adding to the algae environment an algicidally effective amount of a compound of the formula wherein R is hydrogen or alkyl having one to eight carbon atoms, inclusive, R is alkyl having one to eight carbon atoms, inclusive, alkynyl having at least one triple bond and three to six carbon atoms, inclusive, cycloalkyl having three to six carbon atoms, inclusive, allyl, phenyl, 3,4-dichlorophenyl or benzyl and R is alkyl having one to eight carbon atoms, inclusive, haloalkyl in which halo is chloro, fluoro, iodo and bromo and having from one to six carbon atoms, inclusive, alkenyl having at least 1 double bond and from two to four carbon atoms, inclusive, or cyclopropyl.

2. The method according to claim 1 in which R is hydrogen, R is alkyl and R is alkyl.

3. The method according to claim 2 in which R is isopropyl and R is ethyl.

4. The method according to claim 2 in which R is nbutyl and R is ethyl.

5. The method according to claim 2 in which R is ethyl and R is ethyl.

6. The method according to claim 2 in which R is sec.-butyl and R is ethyl.

7. The method according to claim 2 in which R is tert.-butyl and R is ethyl.

8. The method according to claim 2 in which R is nbutyl and R is isopropyl.

9. The method according to claim 2 in which R is tert.-butyl and R is sec.-amyl.

10. The method according to claim 2 in which R is l,2,2-trimethylpropyl and R is ethyl.

11. The method according to claim 2 in which R is n-amyl and R is ethyl.

12. The method according to claim 2 in which R is methyl and R is methyl.

13. The method according to claim 2 in which R is sec.-amyl and R is ethyl.

14. The method according to claim 2 in which R is 1,3-dimethylbutyl and R is ethyl.

15. The method according to claim 2 in which R is l-methylbutyl and R is ethyl.

16. The method according to claim 2 in which R is isobutyl and R is ethyl.

17. The method according to claim 2 in which R is isopropyl and R is 1,1-dimethylbutyl.

18. The method according to claim 2 in which R is tert.-butyl and R is 1,1-dimethylbutyl.

19. The method according to claim 1 in which R is hydrogen, R is cycloalkyl and R is alkyl.

20. The method according to claim 19 in which R is cyclohexyl and R is ethyl.

21. The method according to claim 19 in which R is cyclopentyl and R is ethyl.

22. The method according to claim 1 in which R is alkyl, R is alkyl and R is alkyl.

23. The method according to claim 22 in which R is n-propyl, R is n-propyl and R is ethyl.

24. The method according to claim 22 in which R is methyl, R is isopropyl and R is ethyl.

25. The method according to claim 22 in which R is ethyl, R is isopropyl and R is ethyl.

26. The method according to claim 22 in which R is ethyl, R is tert.-butyl and R is ethyl.

27. The method according to claim 1 in which R is hydrogen, R is 3,4-dichlorophenyl and R is ethyl.

28. The method according to claim 1 in which R is hydrogen, R is alkyl and R is cyclopropyl.

29. The method according to claim 28 in which R is n-butyl.

30. The method according to claim 1 in which R is hydrogen, R is alkyl and R is alkenyl.

31. The method according to claim 30 in which R is n-buty] and R is 2-methylvinyl.

32. The method according to claim 1 in which R is hydrogen, R is alkyl and R is haloalkyl.

33. The method according to claim 32 in which R is n-butyl and R is trichloromethyl.

34. The method according to claim 32 in which R is ethyl and R is trichloromethyl.

35. The method according to claim 32 in which R is isopropyl and R is l-chloroethyl.

36. The method according to claim 1 in which R is hydrogen, R is alkynyl and R is alkyl.

37. The method according to claim 36 in which R is l,l-dimethylprop-2ynyl and R is ethyl.

38. The method according to claim 1 in which R is alkyl, R is alkynyl and R is alkyl.

39. The method according to claim 38 in which R is methyl, R is l-methylprop-Z-ynyl and R is ethyl. 

2. The method according to claim 1 in which R1 is hydrogen, R2 is alkyl and R is alkyl.
 3. The method according to claim 2 in which R2 is isopropyl and R is ethyl.
 4. The method according to claim 2 in which R2 is n-butyl and R is ethyl.
 5. The method according to claim 2 in which R2 is ethyl and R is ethyl.
 6. The method according to claim 2 in which R2 is sec.-butyl and R is ethyl.
 7. The method according to claim 2 in which R2 is tert.-butyl and R is ethyl.
 8. The method according to claim 2 in which R2 is n-butyl and R is isopropyl.
 9. The method according to claim 2 in which R2 is tert.-butyl and R is sec.-amyl.
 10. The method according to claim 2 in which R2 is 1,2,2-trimethylpropyl and R is ethyl.
 11. The method according to claim 2 in which R2 is n-amyl and R is ethyl.
 12. The method according to claim 2 in which R2 is methyl and R is methyl.
 13. The method according to claim 2 in which R2 is sec.-amyl and R is ethyl.
 14. The method according to claim 2 in which R2 is 1,3-dimethylbutyl and R is ethyl.
 15. The method according to claim 2 in which R2 is 1-methylbutyl and R is ethyl.
 16. The method according to claim 2 in which R2 is isobutyl and R is ethyl.
 17. The method according to claim 2 in which R2 is isopropyl and R is 1,1-dimethylbutyl.
 18. The method according to claim 2 in which R2 is tert.-butyl and R is 1,1-dimethylbutyl.
 19. The method according to claim 1 in which R1 is hydrogen, R2 is cycloalkyl and R is alkyl.
 20. The method according to claim 19 in which R2 is cyclohexyl and R is ethyl.
 21. The method according to claim 19 in which R2 is cyclopentyl and R is ethyl.
 22. The method according to claim 1 in which R1 is alkyl, R2 is alkyl and R is alkyl.
 23. The method according to claim 22 in which R1 is n-propyl, R2 is n-propyl and R is ethyl.
 24. The method according to claim 22 in which R1 is methyl, R2 is isopropyl and R is ethyl.
 25. The method according to claim 22 in which R1 is ethyl, R2 is isopropyl and R is ethyl.
 26. The method according to claim 22 in which R1 is ethyl, R2 is tert.-butyl and R is ethyl.
 27. The method according to claim 1 in which R1 is hydrogen, R2 is 3,4-dichlorophenyl and R is ethyl.
 28. The method according to claim 1 in which R1 is hydrogen, R2 is alkyl and R is cyclopropyl.
 29. The method according to claim 28 in which R2 is n-butyl.
 30. The method according to claim 1 in which R1 is hydrogen, R2 is alkyl and R is alkenyl.
 31. The method according to claim 30 in which R2 is n-butyl and R is 2-methylvinyl.
 32. The method according to claim 1 in which R1 is hydrogen, R2 is alkyl and R is haloalkyl.
 33. The method according to claim 32 in which R2 is n-butyl and R is trichloromethyl.
 34. The method according to claim 32 in which R2 is ethyl and R is trichloromethyl.
 35. The method according to claim 32 in which R2 is isopropyl and R is 1-chloroethyl.
 36. The method according to claim 1 in which R1 is hydrogen, R2 is alkynyl and R is alkyl.
 37. The method according to claim 36 in which R2 is 1,1-dimethylprop-2-ynyl and R is ethyl.
 38. The method according to claim 1 in which R1 is alkyl, R2 is alkynyl and R is alkyl.
 39. The method according to claim 38 in which R1 is methyl, R2 is 1-methylprop-2-ynyl and R is ethyl. 